CN106007369A

CN106007369A - Enhancement type glass fiber composition

Info

Publication number: CN106007369A
Application number: CN201610308889.9A
Authority: CN
Inventors: 牛爱军; 徐士明; 崔宝山; 刘海深; 刘兴月
Original assignee: Shandong Fiberglass Group Co Ltd
Current assignee: Shandong Fiberglass Group Co Ltd
Priority date: 2016-05-11
Filing date: 2016-05-11
Publication date: 2016-10-12
Anticipated expiration: 2036-05-11
Also published as: CN106007369B

Abstract

The invention belongs to the technical field of glass fiber and relates to an enhancement type spinning high-strength and high-modulus glass fiber composition applied to the fields of electromechanics, chemical engineering, aircrafts and the like. The enhancement type spinning glass fiber composition is prepared from, by weight, 56-65% of SiO2, 15-21% of Al2O3, 9-18% of MgO, 5-13% of CaO, 0.1-4% of Y2O3, 0-0.8% of Li2O, 0.1-1% of K2O+Na2O, and 3% or less of other impurities. The enhancement type glass fiber composition is prepared through a tank furnace technological process, by means of optimization and combination of the oxide components and particularly the introduction of Y2O3, the melting temperature, the clarification temperature and the shaping temperature of the enhancement type glass fiber composition are reduced under the situation that high strength and high modulus are guaranteed, the temperature difference between the shaping temperature and the liquidus temperature is increased, the wiredrawing situation is improved, and the enhancement type glass fiber composition is beneficial to the industrial production of high-strength and high-modulus fibers.

Description

A kind of enhancement mode glass fiber compound

Technical field:

The invention belongs to glass fibre preparing technical field, relate to the glass of the high strength and modulus of a kind of enhancement mode weaving formula Glass fiber composition, can be used for the fields such as electromechanics, chemical industry and airborne vehicle as a kind of novel material.

Background technology:

Glass fibre is the Inorganic Non-metallic Materials of a kind of excellent performance, the reinforcing material that is generally used in composite, Electrically insulating material and the national economy every field such as heat-insulating material, circuit substrate.High-strength high-modulus glass fiber is initial For defence and military field, along with science and technology development, present high-strength high-modulus glass fiber be also widely used in wind blade, High-pressure bottle, offshore oil pipeline, automobile and aviation field.Typical high strength and modulus glass mainly has S-glass, T glass Glass, the glass being made up of silicon, aluminum and magnesium oxide, this glass has higher intensity and modulus than traditional E glass fibre. Consisting of of existing S-glass fibre: 64～the SiO of 66%₂, 24～the Al of 25%₂O₃, 9.5～the MgO of 10%；T glass fibers Consisting of of dimension: the SiO of 65%₂, the Al of 23%₂O₃, the MgO of 11%；But S-glass, T glass production difficulty are very big, need to make Produce with the crucible of platinum lining, be not suitable for large-scale industrial production and application popularization.To this end, some glass fibre produce Business uses addition TiO₂、Li₂O、B₂O₃, the oxide such as CeO, reduce glass melting temperature and improve fibre forming performance.China Number of patent application is that CN201080070857.0 discloses a kind of high strength glass compositions and fiber, consisting of: 56～ The SiO of 61%₂, 16～the Al of 23%₂O₃, 8～the MgO of 12%, 6～the CaO of 10%, 0～the Li of 1%₂O, 0～the Na of 2%₂O。 This glass is owing to adding higher Al₂O₃, cause liquidus temperature higher, in an embodiment, from 1240～1350, molten Change and be more up to more than 1500 DEG C with clarifying temp；It is a kind of high-strength that Chinese Patent Application No. is that CN200910104239.2 discloses Degree high-modulus glass fiber, consisting of: 56～the SiO of 64%₂, 13～the Al of 20%₂O₃, 7～the MgO of 12%, 8～13% CaO, 0～the TiO of 2.5%₂, 0～the ZrO of 2%₂, 0～the K of 1%₂O+Na₂O content, this glass adds TiO₂, cause glass Glass yellowish, is restricted in some sector application.It is simultaneously introduced ZrO₂, cause, when wire drawing shapes, being susceptible to Devitrification phenomenon；Chinese Patent Application No. is that CN201180037080.2 discloses a kind of high-strength high-modulus glass fiber combination Thing, consisting of: 74～the SiO of 80%₂, 5～the Al of 9.5%₂O₃, 8.75～the MgO of 14.75%, 0～the CaO of 3%, 2～ The Li of 3.25%₂O, 0～the Na of 2%₂O；This glass employs the SiO of very high percentage₂, make forming temperature reach 1400 DEG C, liquid phase Temperature reaches 1457 DEG C, causes forming temperature and liquidus temperature too high, and forming temperature is less than liquidus temperature simultaneously, is unfavorable for glass The drawing of fiber；Chinese Patent Application No. is that CN201180037104.4 discloses a kind of high-strength high-modulus glass fiber combination Thing, consisting of: 60～the SiO of 73.01%₂, 13～the Al of 26%₂O₃, 5～the MgO of 12.75%, 3.25～the CaO of 4%, 3.24～the Li of 4%₂O, 0～the Na of 0.75%₂O；This glass adds higher LiO₂, strength of glass is had reduction effect, also Refractory material is produced bigger erosion, generates heterogeneity glass with refractory material, simultaneously because extremely low CaO/MgO ratio, Glass easily produces devitrification phenomenon, is unfavorable for the drawing of fiber.So, develop a kind of novel glass fiber material and have extensively Application prospect.

Summary of the invention:

It is an object of the invention to the shortcoming overcoming prior art to exist, seek a kind of enhancement mode glass fiber compound, Can be in the case of ensureing glass fiber high-strength degree high-modulus, it is achieved relatively low fusion temperature, forming temperature and liquidus temperature, Obtain wider wire drawing forming temperature scope, the beneficially drawing of fiber simultaneously, be suitable to the kiln with producing E glass fibre raw Produce, to realize heavy industrialization.

To achieve these goals, the enhancement mode glass fiber compound that the present invention relates to includes following percentage by weight Component: the SiO of 56%～65%₂；The Al of 15%～21%₂O₃；The MgO of 9%～18%；The CaO of 5%～13%；0.1%～ The Y of 4%₂O₃；The Li of 0%～0.8%₂O；The K of 0.1%～1%₂O+Na₂O；The composition of other impurity is less than 3%, and total amount is 100%；Existing common tank furnace technical matters is used to be processed into, for dynamo-electric, chemical industry and the preparation of space flight equipment.

In the enhancement mode glass fiber compound that the present invention relates to, SiO₂It is the main oxides forming glass skeleton, tool There is the function of stable component；SiO₂Content can affect strength of glass less than 56%, fusing and clarification temperature can be caused higher than 65% Spend height, preferred SiO₂Content range is 58～63%；Al₂O3 is one of framework oxide forming glass, it is possible to stop glass Glass split-phase and hydrolysis, improve glass modulus；Al₂O₃The too low meeting of content causes glass modulus to decline, too high, causes in glass viscosity Rise, be unfavorable for glass clarifying and homogenizing, preferred Al₂O₃Content range is 16～19%；MgO advantageously reduces the fusing of glass The fusing of temperature, beneficially fiber and shaping, it is possible to increase glass modulus, the content of MgO is too low, is unfavorable for improving glass modulus, The too high glass phase-separating that then increases is inclined to, and preferred content of MgO scope is 10～14%；CaO advantageously reduces the fusing temperature of glass The fusing of degree, beneficially fiber and shaping, the content of CaO is too low, causes fusion temperature too high, fibre forming difficulty, too high, drops Low glass modulus, preferred CaO content scope is 8～11%；Y₂O₃Introducing can significantly reduce the high temperature viscosity of glass, favorably In clarification and the homogenizing of glass, reduce the liquidus temperature of glass simultaneously, increase the temperature of glass forming temperature and liquidus temperature Difference, Y₂O₃Glass modulus, Y can be improved₂O₃Content range be preferably 0.5～1.5%；LiO₂Effect be to flux, glass can be reduced The fusion temperature of glass, improves high temperature viscosity, simultaneously because of its ion relative to otheralkali metal ion for, radius is little, and field intensity is big, energy Improve glass modulus, but too high, strength of glass, LiO can be reduced₂Content range be preferably 0.1～0.6%；K₂O+Na₂O makees For flux, reducing glass melting temperature and high temperature viscosity, introduction volume too much can reduce strength of glass and modulus, K₂O+Na₂O's Content range is preferably 0.1～0.6%.

In the enhancement mode glass fiber compound that the present invention relates to, the Fe of other impurity components₂O₃Miscellaneous as frit Matter introduces, it is not necessary to additionally add；In the case of not damaging glass performance, also include ZnO, TiO₂、ZrO₂、CeO、La₂O₃、SO₃、 B₂O₃With one or more of F, wherein, the total weight percent of these components is less than 3%, preferably less than 2%.

The preparation method of enhancement mode glass fiber compound of the present invention be preferably tank furnace method produce, specifically according to Prepared by lower technique: by each raw material according to component proportion after, mix homogeneously adds tank furnace, molten under conditions of 1400～1650 DEG C Change, clarify and after homogenizing, i.e. obtain glass；Gained glass is flowed out through porous platinum bushing plate, carries out after wetting agent coating again Draw with wire drawing machine, i.e. obtain enhancement mode glass fiber compound.

The present invention compared with prior art, by each oxide component preferably with combination, particularly introduce Y₂O₃, In the case of ensureing high intensity and high-modulus, its fusion temperature, clarifying temp reduce with forming temperature, increase forming temperature and liquid The temperature difference of liquidus temperature, improves wire-drawing operation situation, is more beneficial for the industrialized production of high strength and modulus fiber.

Detailed description of the invention:

Below by embodiment, technical scheme is described in detail.

Embodiment 1:

The present embodiment each component total content is slightly lower than 100%, is interpreted as that residual volume is that trace impurity maybe can not analyze Composition；Concrete preparation process is as follows: each raw material carries out proportioning according to the component of table 1, puts into platinum crucible after mix homogeneously, Melt at 1550～1600 DEG C and be incubated totally 3 hours, obtained glass being poured into water, makes cullet, add after drying Crucible furnace, and flow out through porous platinum bushing plate, draw with wire drawing machine again after carrying out wetting agent coating, i.e. obtain glass fibre group Compound precursor cake or yarn group, recycling conventional method carries out deep processing to meet the expected requirements；Use high temp glass viscometer, root Measure according to the operation sequence of ASTM C-1351M and shape viscosity (log3 temperature)；In platinum-alloy ship, by glass is exposed to Lower 8 hours of isothermal gradient, measures crystallize length and can calculate liquidus temperature；According to ASTM D 2343 detect non-twist slightly The mechanical property of yarn；Table 1 lists concrete 10 embodiment component, and its numbering is respectively 1～10, and comparative example is E glass and S Glass, in table 1, each content of glass fiber compound is all expressed in weight percent.

Table 1 is each embodiment and comparative example composition proportion and performance

10 products in the present embodiment have all reached the requirement of goal of the invention, and parameters all embodies enhancement mode weaving Formula processing preparation characteristic and products thereof advantage performance.

Claims

1. an enhancement mode weaving formula glass fiber compound, it is characterised in that include following components in percentage by weight: 56% ～the SiO of 65%₂；The Al of 15%～21%₂O₃；The MgO of 9%～18%；The CaO of 5%～13%；The Y of 0.1%～4%₂O₃； The Li of 0%～0.8%₂O；The K of 0.1%～1%₂O+Na₂O；The composition of other impurity is not more than 3%, and total amount is 100%；Use Existing common tank furnace technical matters is processed into, for electromechanics, chemical industry, the preparation of space flight equipment.

Enhancement mode glass fiber compound the most according to claim 1, it is characterised in that SiO₂It is the master forming glass skeleton Want oxide, there is the function of stable component, SiO₂Content can affect strength of glass less than 56%, can cause higher than 65% melting Change too high with clarifying temp, preferred SiO₂Content range is 58～63%；Al₂O₃It is one of framework oxide forming glass, Glass phase-separating and hydrolysis can be stoped, improve glass modulus, Al₂O₃Content is that too low meeting causes glass modulus to decline, too high, makes Become glass viscosity to rise, be unfavorable for glass clarifying and homogenizing, preferred Al₂O₃Content range is 16～19%；MgO is conducive to fall The fusing of the fusion temperature of low glass, beneficially fiber and shaping, it is possible to increase glass modulus, the content of MgO is too low, is unfavorable for Improving glass modulus, the too high glass phase-separating that then increases is inclined to, and preferred content of MgO scope is 10～14%；CaO advantageously reduces The fusing of the fusion temperature of glass, beneficially fiber and shaping, the content of CaO is too low, causes fusion temperature too high, fibre forming Difficulty, too high then reduction glass modulus, preferred CaO content scope is 8～11%；Y₂O₃Introducing can significantly reduce glass The clarification of high temperature viscosity, beneficially glass and homogenizing, reduce the liquidus temperature of glass simultaneously, increases glass forming temperature and liquid The temperature difference of liquidus temperature, Y₂O₃Glass modulus, Y can be improved₂O₃Content range be preferably 0.5～1.5%；LiO₂Effect be to help Molten, the fusion temperature of glass can be reduced, improve high temperature viscosity, simultaneously because of its ion relative to otheralkali metal ion for, radius Little, field intensity is big, can improve glass modulus, but too high, can reduce strength of glass, LiO₂Content range be preferably 0.1～ 0.6%；K₂O+Na₂O as flux, reduces glass melting temperature and high temperature viscosity, introduction volume too much can reduce strength of glass and Modulus, K₂O+Na₂The content range of O is preferably 0.1～0.6%；The Fe of other impurity components₂O₃Impurity as frit Introduce, it is not necessary to additionally add；In the case of not damaging glass performance, also include ZnO, TiO₂、ZrO₂、CeO、La₂O₃、SO₃、 B₂O₃With one or more of F, the total weight percent of these components is less than 3%, preferably less than 2%.

Enhancement mode the most according to claim 2 weaving formula glass fiber compound, it is characterised in that described glass fibre group The preparation of compound specifically comprises the processes of: each raw material is added tank furnace according to component proportion mix homogeneously, at the bar of 1400～1650 DEG C Melt under part, clarify and obtain glass after homogenizing；Gained glass is flowed out through porous platinum bushing plate, after carrying out wetting agent coating Enhancement mode glass fiber compound is obtained again with wire drawing machine traction.